CN101743259B - Process for producing vinyl resin - Google Patents
Process for producing vinyl resin Download PDFInfo
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- CN101743259B CN101743259B CN2008800246023A CN200880024602A CN101743259B CN 101743259 B CN101743259 B CN 101743259B CN 2008800246023 A CN2008800246023 A CN 2008800246023A CN 200880024602 A CN200880024602 A CN 200880024602A CN 101743259 B CN101743259 B CN 101743259B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/08—Vinylidene chloride
Abstract
A process for producing a vinyl resin by suspension-polymerizing a vinyl compound with a polymerization tank equipped with a reflux condenser. Uniform vinyl polymer particles are obtained by the process, and the dry foam which generates during the middle to later stage of the polymerization can be highly easily removed. The process comprises conducting the suspension polymerization of a vinyl compound in the presence of a dispersion stabilizer for suspension polymerization with a polymerization tank equipped with a reflux condenser, and is characterized by adding 0.001-5 parts by weight of a vinyl alcohol polymer (A) per 100 parts by weight of the vinyl compound at the time when the conversion into polymer has reached 10% or higher, the polymer (A) having an unsaturated double bond, optionally carboxylated aromatic group, carboxylated saturated aliphatic group, or C11 or higher saturated aliphatic group in side chains.
Description
Technical field
The present invention relates to make by the suspension polymerization of vinyl based compound the method for vinyl resin, this method is used the polymerization tank with reflux exchanger of productivity excellence.In more detail, relate to gained vinyl chloride-based polymer particle evenly, to the manufacture method of the vinyl resin of the defoaming excellence of the dry foam that in polymerization tank, produces in polymerization mid-term～later stage.
Background technology
Recently, in the production of vinyl resins such as polyvinyl chloride, in order to improve productivity, require to shorten every batch of needed time of polymerization, for the speed of removing that increases polymerization reaction heat proposed to use the method for the polymerization tank with reflux exchanger, in order to shorten the method (hot feed method) that the heating-up time has proposed to add the aqueous medium that heated in advance.But, use when having the polymerization tank of reflux exchanger, along with the condensation of gas of vinyl based compound (monomer), near the pressure the reflux exchanger reduces, and therefore has the problem that the generation of wet foam or dry foam becomes violent.Wet foam mainly is that to result from the water of polyvinyl alcohol be the foaming of principal constituent.On the other hand, dry foam refers to that with polyvinyl chloride (PVC) or vinyl chloride monomer (VCM) be the foaming of principal constituent, mainly polymerization the mid-term～later stage produces.The dry foam that produces cover add the liquid layer portion surface of mixture and swim.Because this bubble does not disappear by stirring yet, therefore the shape with blister directly supplies in polymerization.Thereby have following problem: (1) in polymerization tank, dirt is attached to the accompanying gas phase portion of bubble and the interface portion of liquid phase portion, causes productivity to reduce; (2) because dirt adheres to, can't carry out the temperature control of polymerization tank; (3) polymkeric substance of generation blister causes the reduction of yield; (4) produce white point, cause the quality of product to reduce; (5) owing to from the sneaking into of the special-shaped particle of blister polymkeric substance, can't obtain uniform particle etc., these problems have the tendency that becomes serious along with the maximization of reflux exchanger.Illustrated when not using reflux exchanger, though do not produce dry foam, to have the problem that polymerization time prolongs, productivity is low.
Countermeasure as the problems referred to above, the amount of removing that patent documentation 1 (Japanese kokai publication hei 2-180908 communique) discloses at the polymerization reaction heat of reflux exchanger is the moment below 10% of total polymerization heat of reaction, adds the method for organosilicon, low saponification deg polyvinyl alcohol etc. such as dimethyl polysiloxane.
Patent documentation 2 (Japanese kokai publication hei 3-212409 communique) discloses in the amount of removing of the polymerization reaction heat of reflux exchanger and has surpassed 10% o'clock of total polymerization reaction heat, and adding saponification deg with respect to vinyl chloride monomer 100 weight parts is that 20～50 moles of %, the polymerization degree are the method for defoamer 0.001～0.01 weight parts such as 200～400 water-insoluble partly-hydrolysed polyvinyl alcohol 0.002～0.007 weight part and dimethyl polysiloxane.
Patent documentation 3 (Japanese kokai publication sho 55-137105 communique) discloses before polymerization begins that to add saponification deg be 60～80% ion modification polyvinyl alcohol.
It is moment of 5～50% that patent documentation 4 (Japanese kokai publication hei 7-179507 communique) discloses at polymerisation conversion, adding saponification deg is that 70～85 moles of % and the polymerization degree are 700～3000 water-soluble poval, and the method for carrying out polymerization 58～70 ℃ temperature range.
In addition, patent documentation 5 (Japanese kokai publication hei 7-53607 communique) discloses that to begin to polymerisation conversion in polymerization be moment of 5～50%, adds saponification deg continuously or successively and be 70～85 moles of % and the polymerization degree and be the method for 700～3000 water-soluble poval.
It is between 30～60% that patent documentation 6 (Japanese kokai publication hei 7-18007 communique) discloses at polymerisation conversion, adds saponification deg and be 75～85 moles of % and the polymerization degree and be the method for 1500～2700 water-soluble poval.
It is between 20～60% that patent documentation 7 (Japanese kokai publication hei 8-73512 communique) discloses at the percent polymerization transformation efficiency, adds saponification deg and be 20～55 moles of %, mean polymerisation degree and be the method for 150～600 partly-hydrolysed polyvinyl alcohol.
It is moment of 30～90% that patent documentation 8 (Japanese kokai publication hei 10-1503 communique) discloses at polymerisation conversion, and adding saponification deg is the method for the following vinyl alcohol system polymer of 85 moles of %.
It is moment of 30～90% that patent documentation 9 (Japanese kokai publication hei 11-116630 communique) discloses at polymerisation conversion, continuously or be divided into and add the method that saponification deg is the following vinyl alcohol system polymer of 85 moles of % more than 2 times.
It is moment more than 30% that patent documentation 10 (TOHKEMY 2001-122910 communique) discloses at polymerisation conversion, and adding saponification deg is that 65 moles of % are above, the polymerization degree is 700 or more and the method for the polyvinyl alcohol resin of satisfied 0.0300≤(3-Y)/X≤0.0330.(X: saponification deg, Y: iodine is colourity)
But the method that patent documentation 1,2 is put down in writing has the easy problem that reduces of generation tamped density violent, vinyl chloride-based resin of dry foam.In addition, therefore the method that patent documentation 3,4,5,6,7 is put down in writing has the problem that polymerization time prolongs, productivity is low owing to do not use reflux exchanger.And then, though the method that patent documentation 8,9,10 is put down in writing is used polymerization tank, the productivity height with reflux exchanger, with regard to the defoaming that suppresses dry foam, also be nowhere near, also residual have dirt to adhere to the problem that waits, and expects further to improve.
Summary of the invention
The object of the present invention is to provide when use has the suspension polymerization of vinyl based compound of polymerization tank of reflux exchanger, gained vinyl based polymer particle evenly, the vinyl resin manufacture method of the defoaming excellence of dry foam that polymerization mid-term～later stage is produced.
The inventor furthers investigate in order to solve above-mentioned problem, found that by have the polymerization tank of reflux exchanger in use, when in the presence of dispersion stabilizer for suspension polymerization, carrying out the suspension polymerization of vinyl based compound, it is moment more than 10% at polymerisation conversion, add 0.001～5 weight part with respect to these vinyl based compound 100 weight parts and have unsaturated double-bond at side chain, the aromatic group that can have carboxyl, have the saturated aliphatic groups of carboxyl or the vinyl alcohol system polymer (A) that carbonatoms is the saturated aliphatic groups more than 11, can solve above-mentioned problem, thereby finish the present invention.
According to the manufacture method of vinyl resin of the present invention, owing to the defoaming excellence of the dry foam that polymerization mid-term～later stage is produced, therefore can improve the productivity of vinyl resin.In addition, owing to can obtain the uniform vinyl based polymer of particle diameter particle, therefore can provide high-quality vinyl resin.
Embodiment
Below explain the present invention.Among the present invention, reflux exchanger is used for removing efficiently the polymerization reaction heat that the suspension polymerization by the vinyl based compound produces.The gas of the unreacting ethylene base system compound (monomer) that is produced by the suspension in the polymerization tank liquefies by reflux exchanger, is back to polymerization tank, thereby removes heat of polymerization.The temperature of the water coolant of reflux exchanger is generally about 10～50 ℃.Usually, the temperature of polymerization tank is controlled except the heat extraction that utilizes reflux exchanger, also and with the temperature of the sleeve pipe that utilizes polymerization tank (jacket) or coil (coil) controls.The amount of removing to the polymerization reaction heat of reflux exchanger is not particularly limited, and is preferably 10～80%, more preferably 20～60% of total polymerization heat of reaction.
The suspension polymerization of vinyl based compound is carried out in the presence of dispersion stabilizer for suspension polymerization.Dispersion stabilizer for suspension polymerization is not particularly limited, for example can enumerate derivatived celluloses such as methylcellulose gum, hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, carboxy methyl cellulose, water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone etc.Wherein, preferably to use saponification deg be 60～95 moles of %, be preferably 68～93 moles of % and the polymerization degree is 200～3500, is preferably 500～2500 polyvinyl alcohol.
Among the present invention, the usage quantity of dispersion stabilizer for suspension polymerization is not particularly limited, is preferably 0.01～5 weight part, more preferably 0.02～2 weight part, 0.02～1 weight part more preferably with respect to vinyl based compound 100 weight parts.During less than 0.01 weight part, when the vinyl based compound was carried out suspension polymerization, polymerization stability reduced sometimes; When surpassing 5 weight parts, the waste liquid muddiness after the suspension polymerization, the situation that chemical oxygen demand (COD) (COD) increases are arranged.
Among the present invention, when use have the polymerization tank of reflux exchanger, when in the presence of dispersion stabilizer for suspension polymerization, carrying out the suspension polymerization of vinyl based compound, it is moment more than 10% at polymerisation conversion, add vinyl alcohol system polymer (A), this vinyl alcohol system polymer (A) has unsaturated double-bond at side chain, can have the aromatic group of carboxyl, the saturated aliphatic groups with carboxyl or carbonatoms is saturated aliphatic groups (the following PVA (A) that abbreviates as sometimes) more than 11.Differently, this with the partly-hydrolysed polyvinyl alcohol that used in the past have the PVA (A) of functional group at side chain by using, the defoaming that suppresses dry foam improves, and dirt adheres to and is inhibited the homogeneity raising of gained vinyl based polymer particle.
This PVA (A) can have the aromatic group that is selected from unsaturated double-bond more than 2 kinds, can has carboxyl, the saturated aliphatic groups with carboxyl and carbonatoms in a part be functional group in the saturated aliphatic groups more than 11.PVA (A) preferably has unsaturated double-bond at side chain, has the aromatic group of carboxyl or has the saturated aliphatic groups of carboxyl.
The amount of the above-mentioned functional group that has as the side chain of PVA (A), the monomeric unit of each PVA (A) be preferably 0.01～50 mole of %, more preferably 0.01～25 mole of %, more preferably 0.02～20 mole of %, most preferably be 0.05～15 mole of %.
The polymerization degree of PVA (A) is preferably more than 200, more preferably 200～3000, more preferably 300～2500.The polymerization degree was less than 200 o'clock, and the inhibition of dry foam is insufficient, and opposite wet foam also can be even more serious; Surpass at 3000 o'clock, the plasticizer absorption of gained vinyl resin reduces sometimes.
Among the present invention, contain in polymer lateral chain as long as unsaturated double-bond, the aromatic group that can have carboxyl, the saturated aliphatic groups with carboxyl or carbonatoms are the saturated aliphatic groups more than 11, then the concrete structure to PVA (A) is not particularly limited.These functional groups also can be by being bonded on the main chain of PVA (A) by ester bond, ehter bond, urethane bond (ウ レ タ ン Knot closes) etc.In addition, these functional groups can be by replacements such as hydroxyls.PVA (A) is from the viewpoint of property easy to manufacture, preferably has following structure, that is, utilize that to have unsaturated double-bond, can have the aromatic group of carboxyl, the saturated aliphatic groups with carboxyl or carbonatoms be the structure that the carboxylic acid cpd of the saturated aliphatic groups more than 11 obtains vinyl alcohol system polymer (B) esterification.
As the carboxylic acid cpd with unsaturated double-bond, can enumerate unsaturated monocarboxylics such as vinylformic acid, methacrylic acid, Ba Dousuan, iso-crotonic acid, 2-pentenoic acid, 4-pentenoic acid, 2-heptenoic acid, 2-octylenic acid, TRANSCINNAMIC ACID, myristoleic acid, hexadecylenic acid, oleic acid, elaidic acid, punicic acid, gadoleic acid, sinapinic acid, Selacholeic acid, linolic acid, linolenic acid, eleostearic acid, therapic acid, arachidonic acid, timnodonic acid, clupanodonic acid, docosahexenoic acid, Sorbic Acid; Unsaturated dicarboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid etc.Carboxylic acid cpd with unsaturated double-bond can be for two or more.When making PVA (A), the carboxylic acid cpd with unsaturated double-bond can be with for example unsaturated acid anhydrides such as maleic anhydride, fumaric acid anhydride, itaconic anhydride, citraconic anhydride; Unsaturated dicarboxylic monos such as maleic acid mono alkyl ester, fumaric acid mono alkyl ester, methylene-succinic acid mono alkyl ester; The form of acid anhydrides such as unsaturated dicarboxylic acid diester such as dialkyl maleate, dialkyl fumarate, methylene-succinic acid dialkyl or ester is used.These carboxylic acid cpds also can use with the form of salt.
As the example of (not containing the alkene unsaturated link(age)) of the carboxylic acid cpd with the aromatic group that can have carboxyl, the example that does not have carboxyl has aromatic monocarboxylates such as toluylic acid, phenylformic acid, P-hydroxybenzoic acid, tolyl acid, Whitfield's ointment; Example with carboxyl has aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid etc.
As the carboxylic acid cpd of the saturated aliphatic groups with carboxyl, can enumerate aliphatic dicarboxylic acids such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, tartrate, oxysuccinic acid; Aliphatic tricarboxylic acids such as citric acid etc.
As having the carboxylic acid cpd that carbonatoms is the saturated aliphatic groups more than 11 (not having carboxyl), can enumerate lauric acid, tetradecanoic acid, palmitinic acid, stearic acid etc., the carbonatoms of the saturated aliphatic groups that this carboxylic acid cpd has is preferably 11～20.
These aromatic carboxy acid compounds can also use with the form of salt when making PVA (A) with the carboxylic acid cpd with saturated aliphatic groups.
Above-mentioned carboxylic acid cpd (particularly aromatic carboxy acid compound and the carboxylic acid cpd with saturated aliphatic groups) is preferably the carboxylic acid (being dicarboxylic acid, tricarboxylic acid etc.) with 2 above carboxyls.
The saponification deg of vinyl alcohol system polymer (B) (the following PVA (B) that abbreviates as sometimes) is preferably 50～99 moles of %, more preferably 60～98 moles of %, 70～95 moles of % more preferably.Saponification deg has the inhibition that can't obtain dry foam and situation about foaming during less than 50 moles of %; Surpass at 99% o'clock, the situation of the plasticizer absorption reduction of gained vinyl resin is arranged.When using saponification deg less than 100% PVA (B), for by importing the different vinyl ester units of the vinyl ester units that originally has with PVA (B) with the esterification of carboxylic acid cpd, preferably select carboxylic acid cpd.By importing the different vinyl ester units of vinyl ester units that has with PVA (B), can further improve the function of PVA (A).
The polymerization degree of PVB (B) is preferably more than 200, more preferably 200～3000, more preferably 300～2500.The polymerization degree was less than 200 o'clock, and insufficient, the opposite wet foam of the inhibition of dry foam becomes more serious sometimes; Surpass at 3000 o'clock, the situation of the plasticizer absorption reduction of gained vinyl resin is arranged.
Among the present invention, PVA (B) can use separately, perhaps different the mixing more than 2 kinds of characteristic can also be used.
Among the present invention, PVA (B) can by adopt mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerization, dispersion copolymerization method etc. in the past known polymerization process be monomer polymerization with vinyl ester, the vinyl ester based polymer saponification of gained is made.Be solution polymerization process, emulsion polymerization and dispersion copolymerization method from the preferred polymerization process of the viewpoint of industry.When carrying out converging operation, can adopt in batches, semi-batch and any continuous polymerization methods.
Be monomer as the vinyl ester that can be used for polymerization, for example can enumerate vinyl-acetic ester, vinyl formate, propionate, sad vinyl acetate, tertiary carboxylic acid vinyl acetate (バ one サ チ Star Network acid PVC ニ Le) etc., wherein from the preferred vinyl-acetic ester of industrial point.
When vinyl ester was the polymerization of monomer, as long as in the scope of not damaging purport of the present invention, can make vinyl ester was monomer and other monomer copolymerization.As operable monomer, for example can enumerate alpha-olefins such as ethene, propylene, n-butene, iso-butylene; Vinylformic acid and salt thereof; Esters of acrylic acids such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, dodecylacrylate, vinylformic acid stearyl; Methacrylic acid and salt thereof; Methyl acrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, methacrylic acid stearyl; Acrylamide, N methacrylamide, N-ethyl acrylamide, N,N-DMAA, diacetone-acryloamide(DAA), acrylamide propanesulfonic acid and salt, acrylamide propyl-dimethyl amine and hydrochlorate thereof or acrylamide derivatives such as its quaternary salt, N hydroxymethyl acrylamide and derivative thereof; Methacrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, Methacrylamide propanesulfonic acid and salt, dimethylaminopropyl methacrylamide and hydrochlorate thereof or methacrylamide derivatives such as its quaternary salt, N-methylol methacrylamide and derivative thereof; Vinyl ethers such as methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ether; Nitrile such as vinyl cyanide, methacrylonitrile; Vinyl halides such as vinylchlorid, vinyl fluoride class; Halo such as vinylidene chloride, vinylidene fluoride vinylidene (Ha ロ ゲ Application PVC ニ リ デ Application) class; Allylic cpd such as allyl acetate, chlorallylene; Unsaturated dicarboxylic acid and salt or its esters such as toxilic acid, methylene-succinic acid, fumaric acid; Vinyl silyl compounds such as vinyltrimethoxy silane; Polyoxyethylene (methyl) acrylate, polyoxypropylene (methyl) acrylate, polyoxyethylene (methyl) acrylamide, polyoxypropylene (methyl) acrylamide, polyoxyethylene (1-(methyl) acrylamide-1,1-dimethyl propyl) ester, polyoxyethylene (methyl) allyl ethers, polyoxypropylene (methyl) allyl ethers, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether etc. contain the monomer of oxyalkylene group; Methylvinyl acetate etc.
In addition, when vinyl ester is the polymerization of monomer, for the polymerization degree of regulating gained vinyl ester based polymer etc., also can make the chain-transfer agent coexistence.Can enumerate aldehydes such as acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde as chain-transfer agent; Ketones such as acetone, methyl ethyl ketone, hexanone, pimelinketone; Thio-alcohols such as 2-hydroxyl sulfur alcohol, dodecyl mercaptans; Halogenated hydrocarbon such as trieline, tetrachloroethylene wherein preferably uses aldehydes and ketone.The addition of chain-transfer agent determines according to the chain transfer constant of the chain-transfer agent that adds and the polymerization degree of target vinyl ester based polymer, is that monomer is preferably 0.1～10 weight % with respect to vinyl ester in general.
Among the present invention, can use is being that monomer is resulting 1 than polymerization of vinyl ester under common more the temperature condition, the PVA that the content of 2-diol bond (1,2-グ リ コ Yi ル Knot closes) is many.1 of this moment, the content of 2-diol bond be preferably 1.9 moles of % above, more preferably 2.0 moles of % above, more preferably 2.1 moles more than the %.
In the saponification reaction of vinyl ester based polymer, can be suitable for employing basic catalysts such as known sodium hydroxide, potassium hydroxide, sodium methylate in the past, perhaps alcoholysis or the hydrolysis reaction of an acidic catalyst such as tosic acid.The employed solvent of saponification reaction can be enumerated alcohols such as methyl alcohol, ethanol; Ester such as methyl acetate, ethyl acetate class; Ketone such as acetone, methyl ethyl ketone; Benzene, toluene etc. are aromatic hydrocarbon based etc., and these materials can use separately or will be used in combination more than 2 kinds.Wherein, use the mixing solutions of methyl alcohol or methyl alcohol and methyl acetate as solvent, it is easier to carry out saponification reaction in the presence of as the sodium hydroxide of basic catalyst, preferably.
PVA (B) can have ionic functional group endways.Ionic functional group can enumerate carboxyl, sulfonic group etc., wherein preferred carboxyl.Also comprise its salt in the ionic functional group, be preferably the viewpoint of water dispersible, preferred as alkali salt from PVA (B).Import the method for ionic functional group as the terminal part at PVA, can use in the presence of thiol-acetic acid, thiohydracrylic acid, 3-sulfydryl-mercaptan compounds such as 1-propanesulfonic acid sodium salt, making vinyl ester such as vinyl-acetic ester is monomer polymerization, with the method for resulting polymers saponification etc.
Among the present invention, PVA (A) for example can followingly obtain: utilize that to have unsaturated double-bond, can have the aromatic group of carboxyl, the saturated aliphatic groups with carboxyl or carbonatoms be that the carboxylic acid of the saturated aliphatic groups more than 11 obtains vinyl alcohol system polymer (B) esterification.
To utilizing above-mentioned carboxylic acid cpd that PVA (B) esterification method is not particularly limited.Its method for example can be enumerated: (i) make PVA (B) in anhydrous solvent, with the method for suspended state and above-mentioned carboxylic acid cpd reaction; (ii) make above-mentioned carboxylic acid cpd with Powdered or be dissolved or dispersed in alcohol such as methyl alcohol, ethanol, propyl alcohol or methyl acetate, ethyl acetate or the water after, mix with pulpous state or pulverous PVA (B), or air atmosphere in carry out the method that heat treated makes its reaction; (iii) above-mentioned carboxylic acid cpd is added in the polyvinyl acetate of pasty state and carries out saponification, the PVA (B) of gained is carried out methods of heating treatment; (iv) use ribbon blender (ribbon Brabender), V-type mixing tank, Henschel mixer etc. with PVA (B) with after above-mentioned carboxylic acid cpd dry type is mixed, utilize banbury mixers, mixing roll, single shaft or biaxial extruder and kneader to carry out method of melting mixing etc.Wherein, preferred (ii) after mixing PVA (B) and above-mentioned carboxylic acid cpd, in nitrogen or air atmosphere, carry out heat treated and make the method for its reaction and the method with PVA (B) and above-mentioned carboxylic acid cpd melting mixing (iv).
In the above-mentioned method (ii), the condition the when mixture of PVA (B) and above-mentioned carboxylic acid cpd is carried out heat treated is not particularly limited, and the temperature during heat treated is preferably 60～190 ℃, more preferably 65～185 ℃, more preferably 70～180 ℃.In addition, the time of heat treated be preferably 0.5～20 hour, more preferably 1～18 hour, more preferably 1～16 hour.
In the above-mentioned method (iv), the temperature when PVA (B) and above-mentioned carboxylic acid cpd are carried out melting mixing is preferably 130～250 ℃, more preferably 140～220 ℃.The carboxylic acid that makes PVA (B) and have a unsaturated double-bond the time in the employed device of melting mixing of being stranded in is preferably 1～15 minute, more preferably 2～10 minutes.
When preventing that PVA (B) and above-mentioned carboxylic acid cpd carried out heat treated PVA decompose, in addition in order to prevent owing in the main chain of PVA, form painted that polyene produces, can in PVA, cooperate normally used softening agent, the temperature when reducing heat treated thus.Softening agent for example can be enumerated polyvalent alcohols such as glycerine, two glycerine, polyoxyethylene glycol, polypropylene glycol, Sorbitol Powder; The compound that addition of ethylene oxide obtains on these alcohol; Water; Carbohydrate; Polyethers; Amide compounds etc., these can use a kind or will be used in combination more than 2 kinds.The usage quantity of these softening agent is generally 1～300 weight part, more preferably 1～200 weight part, 1～100 weight part more preferably with respect to PVA (B) 100 weight parts.
When PVA (B) and above-mentioned carboxylic acid cpd are carried out heat treated, when containing alkalimetal ion with respect to PVA (B) 100 weight parts with the ratio of 0.003～3 weight part, owing to can suppress the thermal degradation when, thermolysis, gelation, painted etc., therefore preferred of PVA (B).Alkalimetal ion for example can be enumerated potassium ion, sodium ion, magnesium ion etc., and these materials mainly exist with the form of the salt of lower fatty acids such as acetic acid, propionic acid, in addition, when PVA (B) has carboxyl or sulfonic group, exists with the form of the salt of these functional groups.Illustrated that the content of the alkalimetal ion among the PVA can utilize the atom light absorption method to measure.
For the esterification of the PVA (B) that promotes to utilize above-mentioned carboxylic acid cpd, can also under the state that is combined with the acidic substance that play a role as catalyzer or alkaline matter, carry out heat treated to PVA (B) and above-mentioned carboxylic acid cpd.Acidic substance for example can be enumerated mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; Organic acids such as formic acid, acetic acid, oxalic acid, tosic acid; Salt such as tosic acid pyridine, ammonium chloride; Lewis acids such as zinc chloride, aluminum chloride, iron trichloride, tindichloride, tin tetrachloride, boron trifluoride ethyl ether complex etc., these can use a kind or will be used in combination more than 2 kinds.In addition, alkaline matter can be enumerated alkali metal hydroxides such as sodium hydroxide, potassium hydroxide; Alkaline carbonate such as yellow soda ash, salt of wormwood; Metal oxide such as barium oxide, silver suboxide; Alkalimetal hydride such as sodium hydride, potassium hydride KH; Alkali metal alkoxide such as sodium methylate, sodium ethylate; Alkali amides such as sodium amide, potassium amide etc., these can use a kind or will be used in combination more than 2 kinds.The use level of these acidic substance and alkaline matter is preferably 0.0001～5 weight part with respect to PVA (B) 100 weight parts usually.
The carboxylic acid cpd that has a unsaturated double-bond when use is during as above-mentioned carboxylic acid cpd, when PVA (B) and carboxylic acid cpd with unsaturated double-bond are carried out heat treated, in order to prevent that this carboxylic acid cpd or PVA (B) from thermopolymerization taking place, generate gel, can cooperate polymerization retarder.It is polymerization retarder, thiodiphenylamine, N that polymerization retarder for example can be enumerated phenol such as quinhydrones, Hydroquinone monomethylether, N-diphenyl-para-phenylene diamine etc.The use level of polymerization retarder is preferably 0.00001～10 weight part, 0.0001～1 weight part more preferably with respect to PVA (B) 100 weight parts.
By utilizing above-mentioned carboxylic acid cpd with PVA (B) esterification, can obtain PVA (A).The modification amount of utilizing above-mentioned carboxylic acid cpd for example can be by utilizing the unreacted carboxylic acid cpd of liquid chromatography for measuring method etc. measure.In addition,, can also measure, analyze from the method for the signal of two keys and measure it by PVA (A) being dissolved in the DMSO-d6 solvent with 1H-NMR when using when having the carboxylic acid cpd of unsaturated double-bond as above-mentioned carboxylic acid.
The modification amount of the above-mentioned carboxylic acid cpd that the utilization of PVA (A) imports by esterification preferably with respect to 1 PVA (B) monomeric unit be 0.01～50 mole of %, more preferably 0.01～25 mole of %, more preferably 0.02～20 mole of %, be more preferably 0.05～15 mole of %.
When PVA (A) is the PVA that PVA (B) esterification is obtained with the carboxylic acid cpd with 2 above carboxyls, water-soluble in order to improve it, also preferably make with the oxyhydroxide of the irrelevant carboxyl of ester bond and 1～3 valency metal, salt, alkoxide, ammonia, ammonium salt, amine salt, amine salt class in any one reaction.
In the suspension polymerization of vinyl based compound, the interpolation of PVA (A) is that the polymerisation conversion of vinyl based compound is the moment more than 10% opportunity.Because PVA (A) adds in the suspension polymerization process, therefore be before polyreaction finishes, to add certainly the latest.Illustrated that the polymerisation conversion when polyreaction finishes is decided by the kind, reaction conditions of the vinyl based compound of institute's polymerization and employed polymerization starter etc., but as long as adds PVA (A) before polymerisation conversion reaches 95%.The interpolation of PVA (A) is preferably 15%～90%, more preferably 18%～87%, is preferably 20%～85% especially opportunity.In addition, before the interior pressure of polymerization tank will begin to reduce or the interior pressure of polymerization tank when foaming that dry foam causes takes place after just having begun to reduce, also preferably add constantly at this.The addition means of PVA (A) is not particularly limited, and can enumerate the method for adding with forms such as organic solvent solutions such as the aqueous solution, aqueous liquid dispersion, methyl alcohol, methanol-water mixing solutionss.The concentration of the solution of PVA (A) is generally 0.01～30 weight %.The temperature of the solution of PVA (A) is not particularly limited, and can be warming up to room temperature or polymerization temperature.The addition of PVA (A) is with respect to for being 0.001～5 weight part in vinyl based compound 100 weight parts of suspension polymerization, being preferably 0.001～0.5 weight part, 0.01～0.1 weight part more preferably.The addition of PVA (A) is during less than 0.001 weight part, and the inhibition of dry foam is insufficient, and when the addition of PVA (A) surpassed 5 weight parts, the loose density of gained vinyl chloride resin becomes too high, and was not preferred.
Among the present invention, PVA (A) can use separately, perhaps also different the mixing more than 2 kinds of characteristic can be used.
As in the vinyl based compound of suspension polymerization, can enumerate the vinyl halides of vinylchlorid etc.; Vinyl ester such as vinyl-acetic ester, propionate; Vinylformic acid, methacrylic acid, their ester and salt; Toxilic acid, fumaric acid, their ester and acid anhydrides; Vinylbenzene, vinyl cyanide, vinylidene chloride, vinyl ether etc.Wherein, preferred especially vinylchlorid.The suspension polymerization of vinylchlorid can be homopolymerization, also can be copolymerization.As can with the monomer of chloroethylene copolymer, can enumerate vinyl ester such as vinyl-acetic ester, propionate; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate; Alpha-olefin such as ethene, propylene; Unsaturated dicarboxylic acid such as maleic anhydride, methylene-succinic acid class; Vinyl cyanide, vinylbenzene, vinylidene chloride, vinyl ether etc.
As the polymerization starter of the suspension polymerization that can be used for the vinyl based compound, can use in the past any oil-soluble catalyst or the water-soluble catalyst of the polymerization that is used for vinyl chloride monomer etc.Oil-soluble catalyst for example can use peroxycarbonates compounds such as di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate diethoxy ethyl ester; The new enanthic acid tert-butyl ester of peroxidation, new peroxide tert-butyl caprate, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester, peroxidation PIVALIC ACID CRUDE (25) uncle polyhexamethylene, peroxidation neodecanoic acid α-peroxidation ester compounds such as cumyl ester; Ethanoyl cyclohexyl sulfonyl-peroxide, 2,4,4-tri-methyl-amyl-2-peroxidation phenylium ester, 3,5, the superoxide of 5-trimethyl acetyl base superoxide, lauroyl superoxide etc.; Azo is two-2,4-methyl pentane nitrile, the two azo-compounds such as (4-2,4-methyl pentane nitriles) of azo etc.As water-soluble catalyst, for example can enumerate Potassium Persulphate, ammonium persulphate, hydrogen peroxide, cumene hydroperoxide etc.These oil-soluble catalysts or water-soluble catalyst can use separately or will be used in combination more than 2 kinds.
When the suspension polymerization of vinyl based compound, can in polymerization reaction system, add other various additives as required.Additive for example can be enumerated polymerization retarders such as polymerization regulators such as aldehydes, halogenated hydrocarbon, thio-alcohol, phenolic compound, sulphur compound, N-oxide compound etc.In addition, can also randomly add pH regulator agent, linking agent etc., can also be also with multiple above-mentioned additive.
When the suspension polymerization of vinyl based compound, can use saponification deg is that the following partly-hydrolysed vinyl alcohol system polymer of 60 moles of % is as the stably dispersing auxiliary.Its addition with respect to dispersion stabilizer for suspension polymerization 100 weight parts be preferably 0.1～120 weight part, more preferably 0.5～110 weight part, be preferably 1～100 weight part especially.The partly-hydrolysed vinyl alcohol system polymer that uses as the stably dispersing auxiliary can also be enumerated at side chain or end and contain the ionic group of 10 moles of following carboxyls of % etc. or the partly-hydrolysed vinyl alcohol system polymer of oxyalkylene group etc. except the partly-hydrolysed vinyl alcohol system polymer of no modification.
In addition, among the present invention, when the suspension polymerization of vinyl based compound, can also use oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, tristearin, oxyethane propylene oxide block copolymer, water soluble emulsifiers such as polyoxyethylene sorbitan mono-laurate, polyoxyethylene oleic acid glyceride, sodium laurate etc.Its addition is not particularly limited, and is 0.01～1.0 weight part with respect to vinyl based compound 100 weight parts preferably.
According to the manufacture method of vinyl resin of the present invention, owing to the defoaming excellence of the dry foam that polymerization mid-term～later stage is produced, therefore can improve the productivity of vinyl resin.In addition, owing to obtain the uniform vinyl based polymer of particle diameter particle, therefore can provide high-quality vinyl resin.
Explain the present invention by the following examples.In following embodiment and comparative example, " part " and " % " represents " weight part " and " weight % " respectively when not specifying.
The following evaluation of carrying out PVA, vinyl chloride-base polymer particle and dry foam generation state.
(analysis of PVA)
(1) mensuration of carboxyl acid modified amount
1g PVA is dissolved among the ion exchanged water 100g, uses the ODS post, use the 0.1M ammonium dihydrogen phosphate aqueous solution as moving phase, carry out HPLC at 30 ℃ and measure.Try to achieve carboxyl acid modified amount by the quantitative result of unreacted carboxylic acid.
(evaluation of vinyl chloride-base polymer particle)
For the vinyl chloride-base polymer particle, utilize following method to measure size-grade distribution and tamped density.
(1) size-grade distribution
Represent on JIS standard sieve 42 mesh sieves and the content of the particle that 200 orders pass through with weight %." on 42 mesh sieves " refer to particle not the sieve aperture by 42 purpose JIS standard sieves, remain on the sieve aperture; The particle content of " on 42 mesh sieves " is more few, and then oversize particle is more few." 200 orders by " refer to that particle passes through the sieve aperture of 200 purpose JIS standard sieves, and the particle content of " 200 orders by " is more few, and then micro mist is more few.Thereby their content is more few, represents that then particle is more even.
A: less than 0.5%
More than the B:0.5% and less than 1%
More than the C:1%
(2) tamped density
Measure according to JIS K6721.
(dry foam produces the evaluation of state)
The dry foam that utilizes following method to estimate in the polymerization tank produces state.
(1) bubbles
Before after polymerization finishes, to unreacted vinyl chloride monomer, removing, by the bubblement in the viewing window observation polymerization tank of autoclave side.Judgement criteria is as described below.
A: almost do not bubble.
B: the situation that foaming is arranged.
C: bubble obviously.
(2) dirty adhesion amount
By visual observation the dirty attachment state that polymer paste is taken out post polymerization groove inwall from polymerization tank is estimated.Judgement criteria is as described below.
A: almost do not have adhering to of dirt.
B: adhering to of dirt arranged.
C: dirt adheres to obviously.
Embodiment 1
(synthetic-heat treated method of PVA (A))
With PVA (B) powder that the polymerization degree is 400, saponification deg is 80 moles of % be added to for 100 parts in 200 parts of methyl alcohol, make its swelling in 4 parts of solution that obtain of dissolving fumaric acid after, under reduced pressure 40 ℃ temperature drying 24 hours.Then, in the nitrogen atmosphere, 125 ℃ of heat treated 2 hours, obtain PVA (A).Carboxyl acid modified amount is 0.36 mole of %.
(suspension polymerization of vinylchlorid)
The PVA that 0.1 part of polymerization degree is 2000, saponification deg is 80 moles of % is dissolved in the deionized water (90L), the preparation dispersion stabilizer, the adding capacity is in the polymerization tank with reflux exchanger of 200L.Then, add 0.1 part of the new enanthic acid tert-butyl ester of peroxidation, the pressure that outgases in polymerization tank reaches 0.0067MPa except behind the deoxidation, adds 100 parts in vinylchlorid, stirs on one side that feeding hot water is warming up to 63 ℃, initiated polymerization in the sleeve pipe.Pressure in polymerization tank when polymerization begins is 1.02MPa.Proceed polymerization, reach for 70% the moment at polymerisation conversion, add the aqueous solution 10L (counting 0.02 part with PVA (A)) of the above-mentioned synthetic PVA through the fumaric acid modification (A).Pressure in polymerization tank reaches the moment of 0.5MPa, stops polymerization, reclaims unreacted monomer, takes out polymer paste, 65 ℃ of following dry evenings, obtains the vinyl chloride-base polymer particle.Evaluation result to the generation state of gained vinyl chloride-base polymer particle and dry foam is shown in table 1.
Embodiment 2～7
Under condition shown in the table 1, carry out heat treated with the PVA shown in the table 1 (B) and carboxylic acid cpd with unsaturated double-bond, in addition synthesize PVA (A) similarly to Example 1, add this PVA (A) in the moment of polymerisation conversion shown in the table 1, the suspension polymerization that all the other carry out vinylchlorid similarly to Example 1 obtains the vinyl chloride-base polymer particle.The evaluation result of vinyl chloride-base polymer particle is shown in table 1.
Comparative example 1
Except not adding PVA (A), carry out the suspension polymerization of vinylchlorid similarly to Example 1, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 1.Oversize particle is many, can't obtain that foaming after uniform polymer particle and the polymerization is many, the dirt on the polymerization tank inner-wall surface adheres to many.
Comparative example 2
Except not using carboxylic acid cpd, carry out outside the heat treated at the powder to PVA (B) under the condition shown in the table 1, the PVA that obtains similarly to Example 1 uses this PVA, carry out the suspension polymerization of vinylchlorid similarly to Example 1, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 1.Oversize particle is arranged, can't obtain bubbling after uniform polymer particle and the polymerization, dirt is attached on the polymerization tank inner-wall surface.
Comparative example 3
Except the carboxylic acid cpd with unsaturated double-bond shown in the use table 1, it is not carried out the heat treated, the PVA that obtains similarly to Example 1, use this PVA, carry out the suspension polymerization of vinylchlorid similarly to Example 1, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 1.Oversize particle is arranged, can't obtain uniform polymer particle, and foaming, dirt are attached on the polymerization tank inner-wall surface after the polymerization.
Comparative example 4
Except at polymerisation conversion being 5% constantly adds the synthetic similarly to Example 2 PVA (A), carry out the suspension polymerization of vinylchlorid similarly to Example 1, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 1.Oversize particle is arranged, can't obtain uniform polymer particle, and the foaming after the polymerization is many, the dirt on the polymerization tank inner-wall surface adheres to many.
Comparative example 5
(synthesizing of methylene-succinic acid modified PVA based polymer (methylene-succinic acid-vinyl alcohol copolymer))
In the 6L reactive tank with stirrer, nitrogen introducing port, reflux exchanger and additive introducing port, add vinyl-acetic ester 1050g, methyl alcohol 1950g, be warming up to 60 ℃ after, by blasting 30 minutes nitrogen, to carrying out the nitrogen displacement in the system.Preparation is dissolved with concentration 20% solution of methylene-succinic acid in methyl alcohol as comonomer, utilizes the bubbling of nitrogen to carry out the nitrogen displacement.Temperature in the above-mentioned reactive tank is adjusted to 60 ℃, behind the 20% methanol solution 2.8ml of interpolation methylene-succinic acid, adds 2, two (isopropyl cyanide) 2.0g of 2 '-azo, initiated polymerization.In the polymerization polymerization temperature is maintained at 60 ℃, adds 20% methanol solution of methylene-succinic acid continuously with 10mL/hr, after 4.5 hours, reach at 50% o'clock at percent polymerization and cool off, stop polymerization.Then, under reduced pressure remove the unreacted vinyl acetate monomer, obtain the methanol solution of modified PVA c.Add NaOH methanol solution (10% concentration) to this methanol solution that is adjusted to 40% and reach 0.02 until alkali mol ratio (mole number of the vinyl ester units among the mole number of NaOH/modified PVA c), carry out saponification.The saponification deg of gained modified PVA is 68 moles of %.
The methanol solution of the modified PVA c that will remove the unreacted vinyl acetate monomer after polymerization and obtain drops in the normal hexane, make modified PVA c precipitation, the modified PVA c that reclaims with acetone solution, it is refining to repeat 3 above-mentioned redeposition, at 60 ℃ of following drying under reduced pressure, obtain the refining thing of modified PVA c afterwards.The modification amount of being tried to achieve by the proton N MR mensuration of this modified PVA c is 1 mole of %.After carrying out saponification with the methanol solution of 0.2 couple of above-mentioned modified PVA c of alkali mol ratio, implement to utilize in 3 days the Soxhlet of the carrying out of methyl alcohol to extract, then carry out drying, obtain the refining thing of modified PVA.JIS K6726 according to conventional methods measures the mean polymerisation degree of this modified PVA, and the result is 520.
By aforesaid operations, obtain the polymerization degree and be 520, saponification deg is that 68 moles of %, modification amount are the methylene-succinic acid modified PVA based polymer of 1.0 moles of %.Use this methylene-succinic acid modified PVA based polymer to carry out the suspension polymerization of vinylchlorid similarly to Example 1, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 1.Oversize particle is arranged, can not get uniform polymer particle, and bubble after the polymerization, dirt is attached on the polymerization tank inner-wall surface.
Embodiment 8
(synthetic-melting mixing method of PVA (A))
Mix 1 part of fumaric acid with respect to 100 parts of dry types of PVA (B) powder that the polymerization degree is 600, saponification deg is 70 moles of %, use ribbon blender melting mixing 3 minutes under 200 ℃ temperature, obtain PVA (A).Carboxyl acid modified amount is 0.41 mole of %.
(suspension polymerization of vinylchlorid)
Except the addition that makes PVA (A) and interpolation opportunity by table 2 the indicating value, carry out the suspension polymerization of vinylchlorid similarly to Example 1, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 2.
Embodiment 9
Except the carboxylic acid cpd shown in the use table 2, carrying out under the condition shown in the table 2 melting mixing, synthetic PVA (A) uses this PVA (A) to carry out the suspension polymerization of vinylchlorid similarly to Example 8 similarly to Example 8, obtains the vinyl chloride-base polymer particle.Evaluation result is shown in table 2.
Comparative example 6
Under the situation of mixing fumaric acid in dry type not, carry out the melting mixing synthetic PVA similarly to Example 8, use this PVA to carry out the suspension polymerization of vinylchlorid similarly to Example 8.Oversize particle is many, can't obtain uniform polymer particle, and bubbles after the polymerization, and dirt is attached on the polymerization tank inner-wall surface.
Embodiment 10
(synthetic-heat treated method of PVA (A))
With PVA (B) powder that the polymerization degree is 500, saponification deg is 80 moles of % be added into for 100 parts make its swelling in the solution that 3 parts of hexanodioic acids of dissolving obtain in 200 parts of methyl alcohol after, under reduced pressure under 40 ℃ temperature dry 24 hours.Then, in nitrogen atmosphere, 120 ℃ of following heat treated 5 hours, obtain PVA (A).Carboxyl acid modified amount is 0.32 mole of %.
(suspension polymerization of vinylchlorid)
The PVA that 0.1 part of polymerization degree is 2400, saponification deg is 80 moles of % is dissolved in the deionized water (90L), and the preparation dispersion stabilizer adds in the polymerization tank with reflux exchanger of capacity 200L.Then, add 0.1 part of the new enanthic acid tert-butyl ester of peroxidation, the pressure that outgases in polymerization tank reaches 0.0067MPa except behind the deoxidation, adds 100 parts in vinylchlorid, stirs on one side that feeding hot water is warming up to 63 ℃, initiated polymerization in the sleeve pipe.Pressure in polymerization tank when polymerization begins is 1.02MPa.Proceed polymerization, reach for 70% the moment at polymerisation conversion, add the aqueous solution 10L (counting 0.02 part with PVA (A)) of the above-mentioned synthetic PVA through the hexanodioic acid modification (A).Pressure in polymerization tank reaches the moment of 0.5MPa, stops polymerization, reclaims unreacted monomer, takes out polymer paste, 65 ℃ of following dry evenings, obtains the vinyl chloride-base polymer particle.Evaluation result to the generation state of gained vinyl chloride-base polymer particle and dry foam is shown in table 3.
Embodiment 11～13
Use except with PVA shown in the table 3 (B) and carboxylic acid cpd, carrying out the heat treated synthetic similarly to Example 10 PVA (A) under the condition shown in the table 3, time point at polymerisation conversion shown in the table 3 adds PVA (A), the suspension polymerization that all the other carry out vinylchlorid similarly to Example 10 obtains the vinyl chloride-base polymer particle.The evaluation result of vinyl chloride-base polymer particle is shown in table 3.
Comparative example 7
Except not adding PVA (A), carry out the suspension polymerization of vinylchlorid similarly to Example 10, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 3.Oversize particle is many, can not get uniform polymer particle, and the foaming after the polymerization is many, and the dirt on the polymerization tank inner-wall surface adheres to many.
Comparative example 8
Except under the condition shown in the table 3 powder of PVA (B) being carried out the PVA that obtains similarly to Example 10 the heat treated under the situation of not using carboxylic acid cpd, use this PVA, carry out the suspension polymerization of vinylchlorid similarly to Example 10, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 3.Oversize particle is arranged, can not get uniform polymer particle, and bubble after the polymerization, dirt is attached on the polymerization tank inner-wall surface.
Comparative example 9
Except not carrying out the heat treated in nitrogen atmosphere, obtain PVA similarly to Example 10, use this PVA, carry out the suspension polymerization of vinylchlorid similarly to Example 10, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 3.Oversize particle is arranged, can not get uniform polymer particle, and the polymerization foaming, dirt is attached on the polymerization tank inner-wall surface.
Comparative example 10
Except at polymerisation conversion being 5% constantly adds the synthetic similarly to Example 10 PVA (A), carry out the suspension polymerization of vinylchlorid similarly to Example 10, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 3.Oversize particle is arranged, can not get uniform polymer particle, and it is many to bubble after the polymerization, the dirt on the polymerization tank inner-wall surface adheres to many.
Embodiment 14
(synthetic-melting mixing method of PVA (A))
Mix 1 part of hexanodioic acid with respect to 100 parts of dry types of PVA (B) powder that the polymerization degree is 550, saponification deg is 70 moles of %, use ribbon mixer melting mixing 3 minutes under 198 ℃ temperature, obtain PVA (A).Carboxyl acid modified amount is 0.31 mole of %.
(suspension polymerization of vinylchlorid)
Except the addition that makes PVA (A) and interpolation opportunity by table 4 the indicating value, carry out the suspension polymerization of vinylchlorid similarly to Example 10, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 4.
Embodiment 15
Except carboxylic acid cpd shown in the use table 4, carrying out synthesizing PVA (A) the melting mixing similarly to Example 14 under the condition shown in the table 4, use this PVA (A) to carry out the suspension polymerization of vinylchlorid similarly to Example 14, obtain the vinyl chloride-base polymer particle.Evaluation result is shown in table 4.
Comparative example 11
Under the situation of mixing hexanodioic acid in dry type not, carry out obtaining PVA the melting mixing similarly to Example 14, use this PVA to carry out the suspension polymerization of vinylchlorid similarly to Example 14.Oversize particle is many, can not get uniform polymer particle, and bubbles after the polymerization, and dirt is attached on the polymerization tank inner-wall surface.
Industrial applicability
When utilization has used the suspension polymerization of the vinyl based compound of the polymerization tank with reflux exchanger to make vinyl resin, under the situation of adding above-mentioned PVA, obtain uniform vinyl chloride-based polymer particle, defoaming excellence of the dry foam that polymerization mid-term～later stage in polymerization tank is produced etc., its industrial evaluation is high.
Claims (5)
1. the manufacture method of vinyl resin, wherein, use has the polymerization tank of reflux exchanger, when in the presence of dispersion stabilizer for suspension polymerization, carrying out the suspension polymerization of vinyl based compound, it is moment more than 10% at polymerisation conversion, add vinyl alcohol system polymer A 0.001～5 weight part with respect to these vinyl based compound 100 weight parts, described vinyl alcohol system polymer A has unsaturated double-bond at side chain, the aromatic group that can have carboxyl, have the saturated aliphatic groups of carboxyl or carbonatoms and be the saturated aliphatic groups more than 11, its polymerization degree is 200～3000
Above-mentioned vinyl alcohol system polymer A is the vinyl alcohol system polymer that vinyl alcohol system polymer B esterification is obtained with carboxylic acid cpd, wherein said carboxylic acid cpd has unsaturated double-bond, can have the aromatic group of carboxyl, the saturated aliphatic groups with carboxyl or carbonatoms is saturated aliphatic groups more than 11
Described have the carboxylic acid cpd of unsaturated double-bond for being selected from vinylformic acid, methacrylic acid, Ba Dousuan, iso-crotonic acid, the 2-pentenoic acid, the 4-pentenoic acid, the 2-heptenoic acid, the 2-octylenic acid, TRANSCINNAMIC ACID, myristoleic acid, hexadecylenic acid, oleic acid, elaidic acid, punicic acid, gadoleic acid, sinapinic acid, Selacholeic acid, linolic acid, linolenic acid, eleostearic acid, therapic acid, arachidonic acid, timnodonic acid, clupanodonic acid, docosahexenoic acid, Sorbic Acid, toxilic acid, fumaric acid, methylene-succinic acid, at least a in citraconic acid and the methylfumaric acid.
2. the manufacture method of vinyl resin according to claim 1, wherein, above-mentioned vinyl alcohol system polymer A has unsaturated double-bond at side chain, has the aromatic group of carboxyl or has the saturated aliphatic groups of carboxyl.
3. the manufacture method of vinyl resin according to claim 1, wherein, the saponification deg of above-mentioned vinyl alcohol system polymer B is 50～99 moles of %.
4. the manufacture method of vinyl resin according to claim 1, wherein, above-mentioned carboxylic acid cpd is the carboxylic acid with 2 above carboxyls.
5. the manufacture method of vinyl resin according to claim 1, wherein, utilizing above-mentioned carboxylic acid cpd is that monomeric unit with respect to 1 above-mentioned vinyl alcohol system polymer B is 0.01～50 mole of % to the modification amount of above-mentioned vinyl alcohol system polymer A modification.
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| JP2007183894 | 2007-07-13 | ||
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| JP2007183893 | 2007-07-13 | ||
| PCT/JP2008/060620 WO2009011187A1 (en) | 2007-07-13 | 2008-06-10 | Process for producing vinyl resin |
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| EP2876116B1 (en) * | 2012-07-19 | 2019-02-20 | Kuraray Co., Ltd. | Dispersion stabilizer for suspension polymerization, and manufacturing method for vinyl resin |
| KR101534399B1 (en) | 2012-12-18 | 2015-07-09 | 주식회사 엘지화학 | Method of preapring polyvinyl chloride resin by suspension polymerization |
| WO2014098360A1 (en) * | 2012-12-18 | 2014-06-26 | (주) 엘지화학 | Method for preparing vinyl chloride-based resin by using suspension polymerization |
| KR101676087B1 (en) * | 2013-09-30 | 2016-11-14 | 주식회사 엘지화학 | Method for preparing PVC comprising control heat aids of reflux condenser |
| JP6525000B2 (en) * | 2014-04-09 | 2019-06-05 | 株式会社クラレ | Method for producing vinyl resin |
| WO2017047616A1 (en) * | 2015-09-15 | 2017-03-23 | 株式会社クラレ | Dispersion stabilizer for crude oil |
| ES2893524T3 (en) * | 2016-09-28 | 2022-02-09 | Kuraray Co | Modified Vinyl Alcohol Polymer Powder Having Reduced Methanol Content and Method for Its Production, and Water-Soluble Film and Packaging Material |
| EP4332127A1 (en) * | 2021-04-27 | 2024-03-06 | Kuraray Co., Ltd. | Vinyl alcohol polymer, powder including same, methods for producing same, paper processing agent, and dispersant for emulsion polymerization |
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| JPS5529579A (en) * | 1979-08-16 | 1980-03-01 | Denki Kagaku Kogyo Kk | Polymerization of vinyl chloride |
| US4388442A (en) * | 1979-10-13 | 1983-06-14 | Denki Kagaku Kogyo Kabushiki Kaisha | Stabilizer or dispersing agent for use in a suspension polymerization of a vinyl compound comprising a modified and partially hydrolyzed anionic polyvinyl alcohol |
| JPS57119902A (en) * | 1981-01-16 | 1982-07-26 | Kuraray Co Ltd | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP2583453B2 (en) * | 1989-08-01 | 1997-02-19 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer with improved plasticizer absorption |
| JP3093351B2 (en) * | 1991-08-06 | 2000-10-03 | 日本合成化学工業株式会社 | Dispersion stabilizer for suspension polymerization of vinyl chloride, its production method and suspension polymerization method of vinyl chloride |
| US5478900A (en) * | 1993-05-07 | 1995-12-26 | Shin-Etsu Chemical Co., Ltd. | Process for preparing vinyl chloride polymer of quality |
| JP3484504B2 (en) * | 1993-12-21 | 2004-01-06 | 東レ株式会社 | Method for producing melt-modified polyvinyl alcohol |
| JP3529857B2 (en) * | 1994-10-07 | 2004-05-24 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization of vinyl compounds |
| JP3474307B2 (en) * | 1995-04-17 | 2003-12-08 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization of vinyl compounds |
| JP4421715B2 (en) * | 1999-10-28 | 2010-02-24 | 日本合成化学工業株式会社 | Method for producing vinyl resin |
| EP1174444B1 (en) * | 2000-07-19 | 2008-05-21 | Kuraray Co., Ltd., Kurashiki Plant | Dispersion stablizer for suspension polymerization of vinyl compound |
| JP4319177B2 (en) * | 2005-08-30 | 2009-08-26 | 電気化学工業株式会社 | Modified polyvinyl alcohol and dispersant using the same |
| WO2007119735A1 (en) * | 2006-04-12 | 2007-10-25 | Kuraray Co., Ltd. | Dispersion stabilizer |
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| EP2177540B1 (en) | 2013-03-20 |
| WO2009011187A1 (en) | 2009-01-22 |
| EP2177540A4 (en) | 2011-01-19 |
| KR101155297B1 (en) | 2012-06-13 |
| CN101743259A (en) | 2010-06-16 |
| KR20100040930A (en) | 2010-04-21 |
| EP2177540A1 (en) | 2010-04-21 |
| ES2415406T3 (en) | 2013-07-25 |
| JP4238287B1 (en) | 2009-03-18 |
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